CN113493624B - Biomass flame retardant, water-based flame retardant coating, and preparation method and application thereof - Google Patents

Biomass flame retardant, water-based flame retardant coating, and preparation method and application thereof Download PDF

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CN113493624B
CN113493624B CN202110849790.0A CN202110849790A CN113493624B CN 113493624 B CN113493624 B CN 113493624B CN 202110849790 A CN202110849790 A CN 202110849790A CN 113493624 B CN113493624 B CN 113493624B
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flame retardant
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flame
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CN113493624A (en
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李胜
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/12—Impregnating by coating the surface of the wood with an impregnating paste
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention relates to a biomass flame retardant, a water-based flame retardant coating, and a preparation method and application thereof, and belongs to the technical field of flame retardant materials. In order to solve the problems that the existing bio-based flame retardant is low in efficiency and cannot meet the use requirement of a flame-retardant coating, the invention provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate and a flame-retardant synergist, wherein the weight ratio of the chitosan to the melamine formaldehyde resin coated ammonium polyphosphate is 1: 1-1: 6, and the weight of the flame-retardant synergist accounts for 4-8% of the total weight of the biomass flame retardant. According to the biomass flame retardant, the MFAPP, the chitosan and the flame retardant synergist are compounded to obtain the flame retardant with the expansion property of integrating a carbon source, an acid source and a gas source, and the biomass flame retardant has the advantages of being small in addition amount, high in efficiency, low in toxicity and the like. The flame retardant coating is added into water-based epoxy resin to prepare a water-based flame retardant coating, and the coating is applied to wood flame retardance, and the flame retardant coating rapidly expands after encountering fire, so that high-efficiency flame retardance can be realized.

Description

Biomass flame retardant, water-based flame retardant coating, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to a biomass flame retardant, a water-based flame retardant coating, and preparation methods and applications thereof.
Background
The flame-retardant coating is a special coating which covers the surface of combustible materials, effectively protects the combustible materials and reduces the fire hazard and the fire burning speed. The flame-retardant coating can ensure that people have enough time to escape and organize rescue when a fire disaster happens, and larger economic and property losses are avoided.
Although the flame retardant used in the traditional flame retardant coating, such as a halogen flame retardant, has good flame retardancy, a large amount of toxic smoke and gas can be released while the flame retardant is used, so that great hidden dangers are brought to the ecological environment and human health. Development of green, nontoxic and renewable flame retardants and application thereof to flame retardant coatings are the development direction of future flame retardant coatings. The biomass resource is a better green, nontoxic and renewable resource, and the design and preparation of the flame retardant by using the biomass material is a hotspot for the development of the flame retardant at present. However, most of the bio-based flame retardants have low efficiency and cannot meet the use requirements of flame retardant coatings.
Disclosure of Invention
In order to solve the problems that the existing bio-based flame retardant is low in efficiency and cannot meet the use requirement of a flame retardant coating, the invention provides a biomass flame retardant, a water-based flame retardant coating, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the biomass flame retardant mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate and a flame retardant synergist, wherein the weight ratio of the chitosan to the melamine formaldehyde resin coated ammonium polyphosphate is 1: 1-1: 6, and the weight of the flame retardant synergist accounts for 4-8% of the total weight of the biomass flame retardant.
Further, the preparation method of the melamine formaldehyde resin coated ammonium polyphosphate comprises the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde, and reacting for 3 hours at 65-80 ℃ under an alkaline condition to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
and (3) adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one, adding absolute ethyl alcohol and deionized water, reacting for 1-2 h at 90 ℃ under an acidic condition, filtering and collecting the obtained substance, washing and drying to obtain melamine formaldehyde resin coated ammonium polyphosphate.
Further, in the step one, the mass ratio of the melamine to the formaldehyde is 1:3, and the alkaline condition is that the pH value of the system is adjusted to 7-9 by using sodium hydroxide.
Further, the mass ratio of the melamine formaldehyde prepolymer to the ammonium polyphosphate in the second step is 1:4, the volume ratio of the absolute ethyl alcohol to the deionized water is 40:60, and the acidic condition is that the pH value of the system is adjusted to 4-6 by hydrochloric acid.
Furthermore, the flame retardant synergist is one or a combination of several of micron organic montmorillonite, superfine silicon dioxide, antimony trioxide or zinc borate.
Furthermore, the particle size of the micron organic montmorillonite is D50 less than 40 μm, the particle size of the superfine silicon dioxide is 20-100 nm, the particle size of the antimony trioxide is 20-30 nm, and the particle size of the zinc borate is 1-2 μm.
The water-based flame-retardant coating comprises the following components in percentage by weight: 5-20 wt.% of biomass flame retardant, 52-69 wt.% of water-based epoxy resin, 18-21 wt.% of water-based curing agent and 0-20 wt.% of deionized water.
The waterborne epoxy resin is E51 epoxy resin; the water-based curing agent is one or a combination of more of diethylenetriamine, triethylene tetramine or diethylaminopropylamine.
Further, the biomass flame retardant is added into the water-based epoxy resin, uniformly stirred at the speed of 300-1000 rmp, added with the water-based curing agent and deionized water, and continuously stirred until uniform.
The invention provides an application of a water-based flame-retardant coating in fire prevention and flame retardance of wood, wherein the water-based flame-retardant coating is used at the rate of 500g/m2The coating amount of (2) is applied to the surface of the wood.
The invention has the beneficial effects that:
the invention provides an environment-friendly biomass flame retardant which has the advantages of small addition amount, high efficiency, low toxicity, environmental protection and the like. In the biomass flame retardant, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) is a flame retardant with a condensed phase flame retardant mechanism and a vapor phase flame retardant mechanism, and releases non-combustible gases such as phosphorus-containing substances, nitrogen dioxide and the like after combustion, so that the flame retardant effect is achieved; the chitosan is a carbon forming agent, and the flame-retardant synergist plays a role in promoting the carbon formation of the carbon layer and enabling the quality of the carbon layer to be better. The MFAPP, the chitosan and the flame retardant synergist are compounded to obtain the flame retardant with the expansion property of integrating a carbon source, an acid source and a gas source.
The biomass flame retardant is added into the water-based epoxy resin to prepare the water-based flame retardant coating, the water-based flame retardant coating is applied to wood flame retardance, the flame retardant coating is rapidly expanded after encountering fire, the oxygen index of the wood can reach 34.9 percent, the vertical combustion passes through UL-94V0 grade, the flame retardant time reaches more than 60min, and the bonding strength reaches 0.36-0.78 MPa. The flame-retardant coating has better thermal stability, and the carbon residue at 800 ℃ reaches 23.9%. The water-based flame-retardant coating provided by the invention has high flame-retardant efficiency, meets the requirements of the flame-retardant coating, has a good flame-retardant protection effect on wood, and also has the advantages of low toxicity, convenience in processing, environmental friendliness and the like.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention. The process equipment or apparatus not specifically mentioned in the following examples are conventional in the art, and if not specifically mentioned, the raw materials and the like used in the examples of the present invention are commercially available; unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) and a flame retardant synergist micron organic montmorillonite OMMT; wherein the weight ratio of the chitosan to the MFAPP is 1:1, and the weight of the micron organic montmorillonite accounts for 4% of the total weight of the biomass flame retardant.
In this example, the degree of deacetylation of chitosan was greater than 95% and there was no molecular weight requirement. The grain size of the micron organic montmorillonite is required to be D50 less than 40 μm.
The preparation method of MFAPP in this example includes the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde according to the mass ratio of 1:3, adjusting the pH value of the system to 7 by using sodium hydroxide, and then reacting for 3 hours in a constant-temperature water bath at 65 ℃ to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one according to the mass ratio of 1:4, adding a proper amount of absolute ethyl alcohol and deionized water, adjusting the pH value of the system to 4 by using hydrochloric acid, reacting for 1h at 90 ℃, filtering, collecting the obtained product, washing and drying for 8h to obtain MFAPP.
The MFAPP prepared in the embodiment is uniformly mixed with the chitosan and the micron organic montmorillonite to obtain the biomass flame retardant.
Example 2
The embodiment provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) and a flame retardant synergist micron organic montmorillonite OMMT; wherein the weight ratio of the chitosan to the MFAPP is 1:2, and the weight of the micron organic montmorillonite accounts for 6% of the total weight of the biomass flame retardant.
In this example, the degree of deacetylation of chitosan was greater than 95% and there was no molecular weight requirement. The grain size of the micron organic montmorillonite is required to be D50 less than 40 μm.
The preparation method of MFAPP in this example includes the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde according to the mass ratio of 1:3, adjusting the pH value of the system to 8 by using sodium hydroxide, and then reacting for 3 hours in a constant-temperature water bath at 70 ℃ to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one according to the mass ratio of 1:4, adding a proper amount of absolute ethyl alcohol and deionized water, adjusting the pH value of the system to 5 by using hydrochloric acid, reacting for 1.5h at 90 ℃, filtering, collecting the obtained product, washing and drying for 8h to obtain the MFAPP.
The MFAPP prepared in the embodiment is uniformly mixed with the chitosan and the micron organic montmorillonite to obtain the biomass flame retardant.
Example 3
The embodiment provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) and a flame retardant synergist micron organic montmorillonite OMMT; wherein the weight ratio of the chitosan to the MFAPP is 1:3, and the weight of the micron organic montmorillonite accounts for 8% of the total weight of the biomass flame retardant.
In this example, the degree of deacetylation of chitosan was greater than 95% and there was no molecular weight requirement. The grain size of the micron organic montmorillonite is required to be D50 less than 40 μm.
The preparation method of MFAPP in this example includes the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde according to the mass ratio of 1:3, adjusting the pH value of the system to 9 by using sodium hydroxide, and then reacting for 3 hours in a constant-temperature water bath at 75 ℃ to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one according to the mass ratio of 1:4, adding a proper amount of absolute ethyl alcohol and deionized water, adjusting the pH value of the system to 6 by using hydrochloric acid, reacting for 2 hours at 90 ℃, filtering, collecting the obtained product, washing and drying for 8 hours to obtain MFAPP.
The MFAPP prepared in the embodiment is uniformly mixed with the chitosan and the micron organic montmorillonite to obtain the biomass flame retardant.
Example 4
The embodiment provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) and flame retardant synergist ultrafine silicon dioxide; wherein the weight ratio of the chitosan to the MFAPP is 1:4, and the weight of the superfine silicon dioxide accounts for 4% of the total weight of the biomass flame retardant.
In this example, the degree of deacetylation of chitosan was greater than 95% and there was no molecular weight requirement. The particle size of the superfine silicon dioxide is 20-100 nm.
The preparation method of MFAPP in this example includes the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde according to the mass ratio of 1:3, adjusting the pH value of the system to 7 by using sodium hydroxide, and then reacting for 3 hours in a constant-temperature water bath at 80 ℃ to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one according to the mass ratio of 1:4, adding a proper amount of absolute ethyl alcohol and deionized water, adjusting the pH value of the system to 4 by using hydrochloric acid, reacting for 1h at 90 ℃, filtering, collecting the obtained product, washing and drying for 8h to obtain MFAPP.
The MFAPP prepared in the embodiment is uniformly mixed with the chitosan and the superfine silicon dioxide to obtain the biomass flame retardant.
Example 5
The embodiment provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) and a flame retardant synergist antimony trioxide; wherein the weight ratio of the chitosan to the MFAPP is 1:5, and the weight of the antimony trioxide accounts for 6% of the total weight of the biomass flame retardant.
In this example, the degree of deacetylation of chitosan was greater than 95% and there was no molecular weight requirement. The particle size of the antimony trioxide is 20-30 nm. The preparation method of MFAPP in this example includes the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde according to the mass ratio of 1:3, adjusting the pH value of the system to 8 by using sodium hydroxide, and then reacting for 3 hours in a constant-temperature water bath at 65 ℃ to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one according to the mass ratio of 1:4, adding a proper amount of absolute ethyl alcohol and deionized water, adjusting the pH value of the system to 5 by using hydrochloric acid, reacting for 1.5h at 90 ℃, filtering, collecting the obtained product, washing and drying for 8h to obtain the MFAPP.
The MFAPP prepared in the embodiment is uniformly mixed with the chitosan and the antimony trioxide to obtain the biomass flame retardant.
Example 6
The embodiment provides a biomass flame retardant, which mainly comprises chitosan, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) and a flame retardant synergist zinc borate; wherein the weight ratio of the chitosan to the MFAPP is 1:6, and the weight of the zinc borate accounts for 8% of the total weight of the biomass flame retardant.
In this example, the degree of deacetylation of chitosan was greater than 95% and there was no molecular weight requirement. The particle size of the zinc borate is 1-2 μm.
The preparation method of MFAPP in this example includes the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde according to the mass ratio of 1:3, adjusting the pH value of the system to 9 by using sodium hydroxide, and then reacting for 3 hours in a constant-temperature water bath at 80 ℃ to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one according to the mass ratio of 1:4, adding a proper amount of absolute ethyl alcohol and deionized water, adjusting the pH value of the system to 6 by using hydrochloric acid, reacting for 2 hours at 90 ℃, filtering, collecting the obtained product, washing and drying for 8 hours to obtain MFAPP.
The MFAPP prepared in this example was mixed with chitosan and zinc borate uniformly to obtain the biomass flame retardant.
Example 7
The embodiment provides a water-based flame retardant coating containing 5 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: 5 wt.% biomass flame retardant prepared in example 2, 69 wt.% E51 waterborne epoxy resin, 21 wt.% waterborne curing agent diethylenetriamine and 5 wt.% deionized water.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at 1000rmp, added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Example 8
The embodiment provides a water-based flame retardant coating containing 10 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: 10 wt.% biomass flame retardant prepared in example 2, 65 wt.% E51 waterborne epoxy resin, 20 wt.% waterborne curing agent diethylenetriamine and 5 wt.% deionized water.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at 1000rmp, added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Example 9
The embodiment provides a water-based flame retardant coating containing 15 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: 15 wt.% biomass flame retardant prepared in example 2, 60 wt.% E51 waterborne epoxy resin, 19 wt.% waterborne curing agent diethylenetriamine and 6 wt.% deionized water.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at 1000rmp, added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Example 10
The embodiment provides a water-based flame retardant coating containing 18 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: example 2 prepared biomass flame retardant 18 wt.%, E51 waterborne epoxy resin 58 wt.%, waterborne curing agent diethylenetriamine 18 wt.%, and deionized water 6 wt.%.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at 1000rmp, added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Example 11
The embodiment provides a water-based flame retardant coating containing 20 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: example 2 prepared biomass flame retardant 20 wt.%, E51 waterborne epoxy resin 52 wt.%, waterborne curing agent diethylenetriamine 20.8 wt.%, and deionized water 7.2 wt.%.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at 1000rmp, added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Example 12
The embodiment provides a water-based flame retardant coating containing 12 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: 12 wt.% biomass flame retardant prepared in example 2, 55 wt.% aqueous epoxy resin E51, 18 wt.% aqueous curing agent triethylene tetramine and 15 wt.% deionized water.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at 300rmp, then added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Example 13
The embodiment provides a water-based flame retardant coating containing 16 wt.% of biomass flame retardant, which comprises the following components in percentage by weight: 16 wt.% biomass flame retardant prepared in example 2, 60 wt.% aqueous epoxy resin E51, 19 wt.% aqueous curing agent diethylaminopropylamine, and 5 wt.% deionized water.
The preparation method of the water-based flame retardant coating comprises the following steps: the biomass flame retardant prepared in example 2 was added to E51 waterborne epoxy resin, stirred uniformly at a speed of 500rmp, then added with the waterborne curing agent and deionized water, and stirred continuously until uniform.
Comparative example 1
The comparative example is only a water-based paint consisting of water-based epoxy resin, a water-based curing agent and deionized water, and comprises the following components in percentage by weight: e51 waterborne epoxy resin 70 wt.%, waterborne curing agent diethylenetriamine 28 wt.% and deionized water 2 wt.%.
The aqueous flame retardant coatings provided in examples 7-11 and the comparative coating provided in comparative example 1 were mixed at 500g/m2The coating amounts of (a) were coated on the surface of wood, and the flame retardancy, adhesive strength, heat release rate and heat release amount of the flame retardant coating were measured, respectively, and the results are shown in tables 1 to 3.
TABLE 1 flame retardancy of aqueous flame retardant coatings after coating wood
Figure GDA0003532950370000081
As can be seen from the comparison of the data in Table 1, the limit oxygen index, the flame-retardant time and the vertical combustion grade of the flame-retardant coating are gradually increased along with the increase of the addition amount of the biomass flame retardant, which indicates that the biological flame retardant and the flame-retardant coating provided by the invention are not easy to combust after being heated, so that wood can be well protected, and the combustibility of the wood is greatly reduced.
TABLE 2 bonding Strength of waterborne flame retardant epoxy coatings
Figure GDA0003532950370000082
As can be seen from the comparison of the data in Table 2, the carbon residue of the flame retardant coating gradually increases with the increase of the addition amount of the biomass flame retardant, which indicates that the water-based flame retardant coating obtains good thermal stability. The biomass flame retardant provided by the invention is an intumescent flame retardant with a carbon source, an acid source and a gas source integrated, melamine formaldehyde resin coated ammonium polyphosphate (MFAPP) is a flame retardant with a condensed phase flame retardant mechanism and a vapor phase flame retardant mechanism, and after combustion, non-combustible gases such as phosphorus-containing substances and nitrogen dioxide are released to play a flame retardant role; the chitosan is a carbon forming agent, and the flame-retardant synergist plays a role in promoting the carbon formation of the carbon layer and enabling the quality of the carbon layer to be better. When the biomass flame retardant is heated, a uniform carbonaceous foam layer can be quickly formed on the surface of the wood, so that the biomass flame retardant has the functions of isolating heat and oxygen, has high flame retardant efficiency and meets the requirements of flame retardant coatings.
The flame retardant belongs to powder, so that the bonding strength of the coating is inevitably reduced after the flame retardant is added, but even if 18% of the flame retardant is added, the bonding strength of the coating can still reach 0.36MPa, which shows that the waterborne flame-retardant epoxy coating provided by the invention can ensure the bonding strength of the coating while obtaining higher flame-retardant performance, and can meet the requirement of the bonding strength of the fireproof coating.
TABLE 3 Heat Release Rate and amount of Heat Release for waterborne flame retardant epoxy coatings
Figure GDA0003532950370000091
As can be seen from the comparison of the data in Table 3, the heat release speed and the heat release amount of the flame retardant coating are reduced along with the increase of the addition amount of the biomass flame retardant, which indicates that the biomass flame retardant and the flame retardant coating provided by the invention can protect wood in a fire, reduce the heat released during combustion, slow down the combustion speed and strive for valuable time for organization escape and rescue.

Claims (9)

1. The biomass flame retardant is characterized by mainly comprising chitosan, melamine formaldehyde resin coated ammonium polyphosphate and a flame retardant synergist, wherein the weight ratio of the chitosan to the melamine formaldehyde resin coated ammonium polyphosphate is 1: 1-1: 6, and the weight of the flame retardant synergist accounts for 4-8% of the total weight of the biomass flame retardant; the flame-retardant synergist is one or a combination of several of micron organic montmorillonite, superfine silicon dioxide, antimony trioxide or zinc borate.
2. The biomass flame retardant according to claim 1, wherein the preparation method of the melamine formaldehyde resin coated ammonium polyphosphate comprises the following steps:
step one, preparing a melamine formaldehyde prepolymer:
mixing melamine and formaldehyde, and reacting for 3 hours at 65-80 ℃ under an alkaline condition to obtain a melamine-formaldehyde prepolymer;
step two, preparing melamine formaldehyde resin coated ammonium polyphosphate:
and (3) adding ammonium polyphosphate into the melamine formaldehyde prepolymer obtained in the step one, adding absolute ethyl alcohol and deionized water, reacting for 1-2 h at 90 ℃ under an acidic condition, filtering and collecting the obtained substance, washing and drying to obtain melamine formaldehyde resin coated ammonium polyphosphate.
3. The biomass flame retardant according to claim 2, wherein the mass ratio of the melamine to the formaldehyde in the first step is 1:3, and the alkaline condition is that the pH of the system is adjusted to 7-9 by using sodium hydroxide.
4. The biomass flame retardant according to claim 2 or 3, wherein the mass ratio of the melamine formaldehyde prepolymer to the ammonium polyphosphate in the second step is 1:4, the volume ratio of the absolute ethyl alcohol to the deionized water is 40:60, and the acidic condition is to adjust the pH of the system to 4-6 with hydrochloric acid.
5. The biomass flame retardant of claim 4, wherein the particle size of the micro organo montmorillonite is D50 < 40 μm, the particle size of the superfine silica is 20-100 nm, the particle size of the antimony trioxide is 20-30 nm, and the particle size of the zinc borate is 1-2 μm.
6. The water-based flame-retardant coating is characterized by comprising the following components in percentage by weight: the biomass flame retardant of any one of claims 1 to 5 comprising 5 to 20 wt.%, the aqueous epoxy resin comprising 52 to 69 wt.%, the aqueous curing agent comprising 18 to 21 wt.%, and the deionized water comprising 0 to 20 wt.%.
7. The water-based flame-retardant coating material according to claim 6, wherein the water-based epoxy resin is E51 epoxy resin; the water-based curing agent is one or a combination of more of diethylenetriamine, triethylene tetramine or diethylaminopropylamine.
8. A preparation method of the water-based flame retardant coating as claimed in claim 6 or 7, characterized in that the biomass flame retardant as claimed in any one of claims 1 to 5 is added into the water-based epoxy resin, stirred uniformly at a speed of 300 to 1000rmp, then added with the water-based curing agent and deionized water, and stirred continuously until uniform.
9. Use of the aqueous flame retardant coating according to claim 6 or 7 for fire and flame retarding wood, wherein the aqueous flame retardant coating is used at a rate of 500g/m2The coating amount of (2) is applied to the surface of the wood.
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